WO2017183876A1 - Plasticizer composition, and resin composition comprising same - Google Patents

Abstract

The present invention relates to a plasticizer composition and resin composition and a method for preparing same and can provide a plasticizer and a resin composition comprising same, wherein the plasticizer can improve physical properties, such as plasticizing efficiency, migration, tensile strength, elongation rate, stress migration, and light stability, which are required from a sheet prescription when the plasticizer is used as a plasticizer of a resin composition, by making improvement on bad physical properties which have occurred due to structural limits.

Description

Plasticizer composition and resin composition containing same

[Citations with Related Applications]

The present invention claims the benefit of priority based on Korean Patent Application No. 10-2016-0049081 filed on Apr. 22, 2016 and Korean Patent Application No. 10-2017-0047831 filed on Apr. 13, 2017, All content disclosed in the literature is included as part of this specification.

[Technical Field]

The present invention relates to a plasticizer composition and a resin composition comprising the same.

Typically, plasticizers react with alcohols to polycarboxylic acids such as phthalic acid and adipic acid to form the corresponding esters. In addition, in consideration of domestic and international regulations on phthalate-based plasticizers that are harmful to humans, research on plasticizer compositions that can replace phthalate-based plasticizers such as terephthalate-based, adipate-based, and other polymer-based plastics is being continued.

On the other hand, regardless of the plastisol industry such as flooring, wallpaper, soft and hard sheets, calendaring industry, extrusion / injection compound industry, there is an increasing demand for such eco-friendly products, quality characteristics, processability and In order to enhance productivity, appropriate plasticizers should be used in consideration of discoloration, transferability, and mechanical properties.

In these various fields of use, plasticizers, fillers, stabilizers, viscosity-reducing agents, dispersants, antifoaming agents, foaming agents, etc. are blended with PVC resins according to the characteristics required for different industries such as tensile strength, elongation, light resistance, transition, gelling or absorption rate. Done.

For example, among the plasticizer compositions applicable to PVC, when the most widely used di (2-ethylhexyl) terephthalate is applied, the hardness or sol viscosity is high and the absorption rate of the plasticizer is relatively high. It was slow, and the performance and stress performance were not good.

Although the hydrogenated material of di (2-ethylhexyl) terephthalate can be considered as an improvement, the plasticization efficiency is improved, while the migration efficiency and thermal stability are poor, and the production cost is increased due to the hydrogenation reaction. Having difficulty with

In order to overcome this problem, a novel material comprising a material having superior physical properties or a novel derivative thereof than the hydrogenated di (2-ethylhexyl) terephthalate di (2-ethylhexyl) 1,4-cyclohexanoate There is a continuing need for the development of composition products, and research on the development of products and uses as an environmentally friendly plasticizer for vinyl chloride resins continues.

The present invention is a plasticizer which can improve the physical properties such as plasticization efficiency, transferability, gelling properties, etc. required for the prescription of calendering sheet, plastisol and extrusion / injection compound as a plasticizer used in the resin composition and a manufacturing method thereof. And to provide a resin composition comprising them.

Specifically, the present invention can improve the performance of the hydrogenation by mixing a certain amount of citrate-based plasticizers in order to solve the problems of the migration and heating loss of the hydrogenated di (2-ethylhexyl) terephthalate, and the economics. In the case of using a single material, it is noted that the use of alkyl having 9 or 10 carbon atoms is excellent in tensile strength and elongation, heating loss, transferability, plasticizer absorption rate and stress transferability. A plasticizer composition comprising a 4-cyclohexane diester-based material and a citrate-based material is provided.

According to an embodiment of the present invention to solve the above problems, one kind of cyclohexane 1,4-diester material; And citrate-based material, wherein the weight ratio of the cyclohexane 1,4-diester-based material and the citrate-based material is 99: 1 to 1:99.

The citrate-based material may include any one selected from the group consisting of a hybrid alkyl substituted citrate-based material having 4 to 10 carbon atoms and a non-hybrid alkyl substituted citrate-based material having 4 to 10 carbon atoms.

The plasticizer composition may further comprise an epoxidized material.

The epoxidized material may further include 1 to 100 parts by weight based on 100 parts by weight of the mixed weight of the cyclohexane 1,4-diester-based material and the citrate-based material.

According to an embodiment of the present invention to solve the above problems, a step of producing a cyclohexane 1,4-diester material by hydrogenation of a terephthalate-based material in the presence of a metal catalyst; And blending the cyclohexane 1,4-diester-based material and the citrate-based material in a weight ratio of 99: 1 to 1:99 to obtain a plasticizer composition, wherein the terephthalate-based material is a mixture. Provided is a method of preparing a plasticizer composition.

According to an embodiment of the present invention to solve the above problems, 100 parts by weight of resin; And 5 to 150 parts by weight of the plasticizer composition of claim 1 is provided.

The resin may be at least one member selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomers.

When used in a resin composition, the plasticizer composition according to an embodiment of the present invention may provide excellent physical properties such as migration resistance and volatility, as well as excellent plasticization efficiency and tensile strength and elongation.

1 is an image showing the improvement of heat resistance according to the addition of the epoxidized material.

Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.

The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

As used herein, the term “butyl” refers to an alkyl group having 4 carbon atoms, and may be used as a term including both straight and branched chains, and may be, for example, n-butyl, isobutyl, or t-butyl. But preferably n-butyl or isobutyl.

As used herein, the terms “octyl” and “2-ethylhexyl” are alkyl groups having 8 carbon atoms, and may be used in combination with octyl as an abbreviation of 2-ethylhexyl, and in some cases, may refer to octyl which is a linear alkyl group. However, it can be interpreted to mean a branched alkyl group, 2-ethylhexyl.

Plasticizer composition

According to one embodiment of the present invention, it is possible to provide a plasticizer composition including one cyclohexane 1,4-diester-based material. Specifically, the cyclohexane 1,4-diester material is 1 to 99% by weight, 20 to 99% by weight, 40 to 99% by weight, 50 to 95% by weight or 60 to 90% by weight based on the total weight of the composition The content selected in the range of the like may be applied.

In the present specification, the cyclohexane 1,4-diester material may be named, for example, dialkyl cyclohexane-1,4-diester when R1 and R2 are the same.

The cyclohexane 1,4-diester-based material is diisononyl cyclohexane-1,4-diester (1,4-DINCH), diisodecyl cyclohexane-1,4-diester (1, 4-DIDCH), di (2-propylheptyl) cyclohexane-1,4-diester (1,4-DPHCH) may be selected.

As described above, when the number of carbon atoms of the alkyl group bonded to the diester is 9 or more, preferably 9 or 10, the transition characteristics and the heating loss can be improved, which may be advantageous in mechanical properties.

In addition, according to an embodiment of the present invention, the plasticizer composition comprises a citrate-based material, the citrate-based material is a mixed alkyl substituted citrate-based material having 4 to 10 carbon atoms and a non-hybridized alkyl substitution having 4 to 10 carbon atoms It may include one or more compounds selected from the group consisting of citrate-based materials.

The mixed alkyl substituted citrate-based material having 4 to 10 carbon atoms may be, for example, 1,2-dibutyl 3- (2-ethylhexyl) 2-hydroxypropane-1,2,3-tricarboxylate, 1,3-dibutyl 2- (2-ethylhexyl) 2-hydroxypropane-1,2,3-tricarboxylate, 1-butyl 2,3-di (2-ethylhexyl) 2-hydroxypropane 4 and 8 carbon atoms, such as -1,2,3-tricarboxylate or 2-butyl 1,3-di (2-ethylhexyl) 2-hydroxypropane-1,2,3-tricarboxylate Citrate having a combination substituent of an alkyl group; 1,2-dipentyl 3-heptyl 2-hydroxypropane-1,2,3-tricarboxylate, 1,3-dipentyl 2-heptyl 2-hydroxypropane-1,2,3-tricarboxyl Rate, 1-pentyl 2,3-diheptyl 2-hydroxypropane-1,2,3-tricarboxylate, or 2-butyl 1,3-diheptyl 2-hydroxypropane-1,2,3- Citrate having a combination substituent of an alkyl group having 5 and 7 carbon atoms, such as tricarboxylate, and the like. In addition to this, a citrate having a combination substituent of two alkyl groups having 4 to 10 carbon atoms and having different carbon atoms may be selected. This may be applied, the alkyl group may be straight or branched chain.

In the non-hybrid alkyl substituted citrate-based material having 4 to 10 carbon atoms, the alkyl group having 4 to 10 carbon atoms may be linear or branched. For example, tributyl citrate (TBC) and tripentyl citrate (TPC). , Trihexyl citrate (THC), triheptyl citrate (THPC), tri (2-ethylhexyl) citrate (TOC), trinonyl citrate (TNC), tri (2-propylheptyl) citrate (TPHC) The butyl group to nonyl group may be applied to each of the structural isomers such as isobutyl group for butyl group, octyl group for 2-ethylhexyl group, isononyl group for nonyl group, and 2-propylheptyl group. In this case, all of isodecyl may be included.

Although not limited thereto, non-hybrid alkyl substituted citrate materials having 4 to 10 carbon atoms may be preferred, compared to hybrid alkyl substituted citrate materials, and tributyl citrate and / or tri (2-ethylhexyl) sheets. The rate may be used at a slightly more frequent frequency.

On the other hand, trialkyl citrate, or dinalkyl-malkyl citrate, such as the hybrid or non-hybrid alkyl substituted citrate compound, may be applied. When the acetyl group is present in the citrate-based material, the physical properties of the plasticizer, particularly There exists a possibility that workability and gelling property may deteriorate with the fall of plasticization efficiency.

In other words, when the citrate-based material is an acetyl citrate compound in which an acetyl group is substituted for hydrogen of the remaining hydroxy group in addition to the three ester groups, the plasticization efficiency is lowered, the amount of plasticizer to be overcome is increased, and the product price is increased. Due to such problems, deterioration in various aspects such as marketability, economic feasibility and physical properties may be a problem.

Here, the cyclohexane 1,4-diester-based material and the citrate-based material in the plasticizer composition, the upper limit is 99: 1, 95: 5, 90:10, 85:15, 80:20, 70 by weight ratio : 30 or 60:40 and the lower limit may be 1:99, 5:95, 10:90, 15:85, 20:80, 30:70 or 40:60. Preferably 90:10 to 20:80, more preferably 90:10 to 30:70.

The plasticizer composition may include a cyclohexane 1,4-diester-based material and a citrate-based material, and may further include an epoxidized material.

In the case of the mixed plasticizer composition of the cyclohexane 1,4-diester-based material and the citrate-based material, among the various physical properties, the heat resistance may not be excellent, and the heat resistance may further include the epoxidized material. This can be supplemented.

The addition amount of the epoxidized material for supplementing the heat resistance property may be 1 to 100 parts by weight based on 100 parts by weight of the mixed weight of cyclohexane 1,4-diester-based material and citrate-based material, preferably 5 to 80 parts by weight Can be. When the epoxidation material is added in the above range, the heat resistance property can be compensated for. However, when the amount of the epoxidized material is added in excess, the cyclohexane 1,4-diester material and the citrate material are relatively low. There is a fear that the physical properties of the basic plasticizer is included, it is necessary to adjust the content.

The epoxidized material is, for example, epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized palm oil (epoxidized stearate), epoxidized oleate, epoxidized tallate and epoxidized linoleate or mixtures thereof. Preferably, epoxidized soybean oil (ESO), epoxidized linseed oil (ELO) and epoxidized ester derivatives thereof may be applied, but are not limited thereto.

Method of Preparation of Plasticizer Composition

According to one embodiment of the invention, the step of hydrogenating the terephthalate-based material in the presence of a metal catalyst to prepare a cyclohexane 1,4-diester-based material; And blending the cyclohexane 1,4-diester-based material and the citrate-based material in a weight ratio of 99: 1 to 1:99 to obtain a plasticizer composition.

The terephthalate-based material is a direct esterification reaction of at least one alcohol selected from the group consisting of 2-ethylhexyl alcohol, isononyl alcohol, 2-propylheptyl alcohol, butyl alcohol and isobutyl alcohol and terephthalic acid; Terephthalate-based materials can be prepared.

The direct esterification may include adding terephthalic acid to an alcohol, then adding a catalyst and reacting under a nitrogen atmosphere; Removing unreacted alcohol and neutralizing unreacted acid; And dehydration and filtration by distillation under reduced pressure.

The alcohol may be used in the range of 150 to 500 mol%, 200 to 400 mol%, 200 to 350 mol%, 250 to 400 mol%, or 270 to 330 mol% based on 100 mol% of terephthalic acid.

On the other hand, the catalyst is, for example, acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, paratoluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, alkyl sulfuric acid, aluminum lactic acid, lithium fluoride, potassium chloride, cesium chloride, Metal salts such as calcium chloride, iron chloride, aluminum phosphate, metal oxides such as heteropolyacids, natural / synthetic zeolites, cation and anion exchange resins, tetraalkyl titanate and organic metals such as polymers thereof. . As a specific example, the catalyst may use tetraalkyl titanate.

The amount of the catalyst used may vary depending on the type, for example, in the case of a homogeneous catalyst, 0.01 to 5% by weight, 0.01 to 3% by weight, 1 to 5% by weight or 2 to 4% by weight based on 100% by weight of the total reactants. And, in the case of heterogeneous catalysts, it may be in the range of 5 to 200%, 5 to 100%, 20 to 200%, or 20 to 150% by weight of the total amount of reactants.

The direct esterification reaction is 10 minutes to 10 hours, preferably 30 minutes to 8 hours, more preferably 1 to 6 hours in the temperature range of 80 ℃ to 270 ℃, preferably 150 ℃ to 250 ℃ It is preferably carried out in, it is possible to effectively obtain a terephthalate-based material in the appropriate temperature, catalyst and time range in consideration of the boiling point of alcohol and the like.

The hydrogenation step may be a step of converting the terephthalate-based material into cyclohexane 1,4-diester-based material by hydrogenation of the terephthalate-based material in the presence of a metal catalyst.

The hydrogenation step is a reaction for removing the aromaticity of the benzene ring of the terephthalate-based materials by adding hydrogen in the presence of a metal catalyst, may be a kind of reduction reaction.

The hydrogenation reaction is a reaction of the terephthalate-based material with hydrogen under a metal catalyst to synthesize a cyclohexane 1,4-diester-based material, the reaction conditions of the benzene without affecting the carbonyl group substituted in the benzene It may include all conventional reaction conditions capable of hydrogenating only the ring.

The hydrogenation reaction may be performed by further including an organic solvent such as ethanol, but is not limited thereto. As the metal catalyst, a Rh / C catalyst, a Pt catalyst, a Pd catalyst, and the like, which are generally used to hydrogenate a benzene ring, may be used. However, the metal catalyst is not limited thereto.

For example, the pressure during hydrogenation in the hydrogenation reaction may be about 3 to 15 MPa, the reaction may be carried out for about 2 to 10 hours, it may be carried out at a temperature of about 80 ℃ to 200 ℃.

The blending may be performed by blending the cyclohexane 1,4-diester-based material and the citrate-based material in which the terephthalate-based material is converted through a hydrogenation reaction in a ratio of 1:99 to 99: 1 by weight. A plasticizer composition may be prepared, wherein the cyclohexane 1,4-diester material is characterized in that it is a single compound.

The citrate-based material may be prepared by a direct esterification reaction of citric acid and one or more alkyl alcohols or a trans esterification reaction of trialkyl citrate and alkyl alcohols. It may be applied equivalently to that applied to the Sein 1,4-diester-based material, and in the case of the trans esterification reaction, the contents as illustrated below may be applied.

As used in the present invention, "trans esterification reaction" refers to a reaction in which an alcohol and an ester react with each other, as shown in Scheme 1 below, so that R of the ester is interchanged with R 'of an alcohol.

Scheme 1

According to an embodiment of the present invention, when the trans-esterification reaction is carried out when the alkoxide of the alcohol attacks the carbon of two ester (RCOOR ″) groups present in the ester compound; When attacking the carbon of one ester (RCOOR ”) group present in the ester compound; In the three cases, three kinds of ester compositions may be generated by water.

In addition, the trans-esterification reaction has the advantage that does not cause a waste water problem compared to the acid-alcohol esterification reaction, and can proceed under a non-catalyst, it can solve the problem when using an acid catalyst.

For example, tri (2-ethylhexyl) citrate and butyl alcohol can be prepared by tri- (2-ethylhexyl) citrate, di (2-ethylhexyl) butyl citrate, dibutyl ( A mixture of 2-ethylhexyl) citrate and tributyl citrate can be produced, wherein the four citrates have 3.0 to 70 weight percent tri (2-ethylhexyl) citrate relative to the total weight of the mixture, Two types of citrate having a mixed alkyl may be formed in an amount of 0.5 wt% to 50 wt%, and tributyl citrate in an amount of 0.5 wt% to 85 wt%, specifically 10 wt% to 50 wt%, 0.5 Weight percent to 50 weight percent, and 35 to 80 weight percent. Within this range, there is an effect of obtaining a citrate-based material (mixture) having high process efficiency and excellent processability and absorption rate.

In addition, the mixture prepared by the trans-esterification reaction can control the composition ratio of the mixture according to the amount of alcohol added.

The addition amount of the alcohol may be 0.1 to 89.9 parts by weight, specifically 3 to 50 parts by weight, and more specifically 5 to 40 parts by weight based on 100 parts by weight of the citrate-based material.

The more the amount of alcohol added, the greater the mole fraction of the citrate participating in the trans-esterification reaction, and thus the citrate produced by attacking only one or two ester groups in the product. The content of citrate attacked by three ester groups may increase.

 Correspondingly, the content of unreacted citrate may tend to decrease.

According to one embodiment of the present invention, the molar ratio of reactant citrate and alcohol is, for example, 1: 0.005 to 5.0, 1: 0.05 to 2.5, or 1: 0.1 to 1.0, within this range, the process efficiency is high and the processability is improved. There is an effect of obtaining an ester plasticizer composition having excellent effects.

However, the composition ratio of the mixture of the three citrate is not limited to the above range, the composition ratio can be changed by adding any one of the three citrate, the possible mixed composition ratio is as described above .

The ester composition prepared by the trans esterification step may include all of the single attack ester compound, the double attack ester compound, and the reaction residual ester compound, and control the composition ratio of the ester composition according to the amount of the alcohol added. can do.

The trans esterification reaction is carried out at a reaction temperature of 120 ° C to 190 ° C, preferably 135 ° C to 180 ° C, more preferably 141 ° C to 179 ° C, for 10 minutes to 10 hours, preferably 30 minutes to 8 hours, more Preferably it is carried out in 1 to 6 hours. It is possible to effectively obtain a mixture that is a terephthalate-based material of a desired composition ratio within the temperature and time range. In this case, the reaction time may be calculated from the time point at which the reaction temperature is reached after the reaction temperature is raised.

The trans esterification reaction may be performed under a non-catalyst, but in some cases, may be performed under an acid catalyst or a metal catalyst, in which case the reaction time may be shortened.

The acid catalyst may be, for example, sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, and the like, and the metal catalyst may be, for example, an organometallic catalyst, a metal oxide catalyst, a metal salt catalyst, or the metal itself.

The metal component may be any one selected from the group consisting of tin, titanium and zirconium, or a mixture of two or more thereof.

In addition, the method may further include distilling off the unreacted alcohol and reaction by-products, for example, an ester compound after the trans-esterification reaction.

The distillation may be, for example, two-stage distillation separately using the boiling point difference of the alcohol and the reaction by-product.

In another example, the distillation may be mixed distillation. In this case, there is an effect that the ester plasticizer composition can be relatively stable at a desired composition ratio. The mixed distillation means distilling butanol and reaction by-products simultaneously.

Since the content, type, and mixing ratio of the cyclohexane 1,4-diester-based material and the citrate-based material mixed during the blending have been described above, the description thereof is omitted.

After the blending, the method may further include adding an epoxidized material. Since the content in the case of adding the said epoxidation material further, and the kind of epoxidation material were mentioned above, the description is abbreviate | omitted.

According to another embodiment of the present invention, there is provided a resin composition comprising the plasticizer composition and the resin described above.

The resin may be a resin known in the art. For example, one or more mixtures selected from ethylene vinyl acetate, polyethylene, polyketone, polypropylene, polyvinyl chloride, polystyrene, polyurethane, thermoplastic elastomer, and polylactic acid may be used, but is not limited thereto.

The plasticizer composition may be included in 5 to 150 parts by weight based on 100 parts by weight of the resin.

However, the content of the plasticizer may be changed according to the method of processing the resin composition. For example, in the case of a resin in which melt processing such as extrusion, injection, or calendering is performed, the plasticizer is preferably 5 to 100 parts by weight of the resin. 100 parts by weight, 5 to 60 parts by weight, or 5 to 50 parts by weight.

In addition, in the case of a resin in which plastisol processing such as spread coating, spray coating or dip coating is performed, a plasticizer may be included as 30 to 150 parts by weight, 40 to 130 parts by weight, and 60 to 120 parts by weight.

The resin composition may further include a filler. The filler may be 0 to 300 parts by weight, preferably 50 to 200 parts by weight, more preferably 100 to 200 parts by weight based on 100 parts by weight of the resin.

The filler may be a filler known in the art, it is not particularly limited. For example, it may be at least one mixture selected from silica, magnesium carbonate, calcium carbonate, hard coal, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate and barium sulfate.

In addition, the resin composition may further include other additives such as stabilizers, if necessary. Other additives such as the stabilizer may be, for example, 0 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the resin.

The stabilizer may be, for example, a calcium-zinc-based (Ca-Zn-based) stabilizer such as calcium stearate salts, but is not particularly limited thereto.

The resin composition may be applied to all resins used for melt processing and plastisol processing, and may be applied to compound industries such as extrusion or injection, calendering and plastisol, for example. Examples of the product may include various electric wires, flooring materials, automotive interior materials, films, sheets, wallpaper, toys, and the like.

Example

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Production Example  One: Diisononyl Cyclohexane -1,4- Diester  Produce

One) Esterification  reaction

498.0 g of purified terephthalic acid (PTA), 1,300 g of isononanol (INA) (molar ratio of PTA: INA (1.0) ): (3.0)), 1.54 g (0.31 parts by weight of 100 parts by weight of PTA) of a titanium catalyst (TIPT, tetra isopropyl titanate) was added as a catalyst, and the temperature was gradually raised to about 170 ° C. The production of water was started at about 170 ° C., and the reaction was carried out for about 4.5 hours while nitrogen gas was continuously added at a reaction temperature of about 220 ° C. and atmospheric pressure. The reaction was terminated when the acid value reached 0.01.

After the reaction is completed, distillation is performed under reduced pressure for 0.5 to 4 hours to remove unreacted raw materials. In order to remove unreacted raw materials below a certain content level, steam extraction is performed under reduced pressure using steam for 0.5 to 3 hours, the reaction solution temperature is cooled to about 90 ° C., and neutralization is performed using an alkaline solution. . In addition, washing with water may be performed, and then the reaction solution is dehydrated to remove moisture. The filtrate was added to the reaction solution from which the water was removed, the resultant was stirred for a while, and then filtered to obtain 1,243 g (yield: 99.0%) of diisononyl terephthalate.

2) hydrogenation reaction

In a 1.5L high pressure reactor, 1000 g of the composition produced by the esterification reaction and 20 g of ruthenium catalyst (NE chemcat) were charged with raw materials, hydrogen was added at a pressure of 8 MPa, and hydrogenation was performed at a temperature of 150 ° C. for 3 hours. , Reaction was completed. After the reaction was completed, the catalyst was filtered, and a mixture composition hydrogenated in a yield of 99% was prepared through a conventional purification process.

Production Example  2: Preparation of di (2-propylheptyl) cyclohexane-1,4-diester

Instead of using isononyl alcohol in esterification in Preparation Example 1, 2-propylheptyl alcohol was used to perform esterification and hydrogenation in the same manner as Preparation Example 1 to obtain a hydrogenated mixed composition.

Production Example  3: manufacture of TBC

384 g of citric acid and 580 g of butanol were used as reaction raw materials, and finally, 706 g (yield: 98%) of tributyl citrate were obtained.

Production Example  4: Of TOC  Produce

Finally, 1,029 g (yield: 98%) of tri-2-ethylhexyl citrate were finally obtained using 384 g of citric acid and 1014 g of 2-ethylhexanol as reaction raw materials.

Production Example  5: TiNC  Produce

As a reaction raw material, 384 g of citric acid and 1,123 g of isononanol were used to finally obtain 1111 g (yield: 98%) of triisobutyl citrate.

Production Example  6: TPHC  Produce

384 g of citric acid and 1,235 g of 2-propylheptanol were used as reaction raw materials, and finally 1,200 g of tri (2-propylheptyl citrate) (yield: 98%) was obtained.

Example  1 to 8 and Comparative example  1 to 10

The structure of the Example and the comparative example was carried out as Table 1 below.

division	Hydrogenated Mixed Composition	Citrate	Mixing ratio
Example 1	1,4-DINCH	TBC	7: 3
Example 2	1,4-DINCH	TBC	3: 7
Example 3	1,4-DINCH	TOC	8: 2
Example 4	1,4-DINCH	TOC	2: 8
Example 5	1,4-DPHCH	TINC	6: 4
Example 6	1,4-DPHCH	TPHC	6: 4
Example 7	1,4-DPHCH	TBC	5: 5
Example 8	1,4-DPHCH	TOC	5: 5
Comparative Example 1	1,4-DEHCH	TOC	5: 5
Comparative Example 2	1,4-DHpCH	TBC	5: 5
Comparative Example 3	1,4-DBCH	TOC	5: 5
Comparative Example 4	1,4-DBenCH	TOC	5: 5
Comparative Example 5	1,4-DCyHCH	TBC	5: 5
Comparative Example 6	1,2-DEHCH	TOC	5: 5
Comparative Example 7	1,2-DINCH	TBC	5: 5
Comparative Example 8	1,2-DPHCH	TBC	5: 5
Comparative Example 9	1,4-DPHCH	-	-
Comparative Example 10	-	TOC	-

Example  9 to 11

In order to confirm the heat resistance improvement using the epoxidized material, Examples 9 to 11 were configured as shown in Table 2 below.

division	Plasticizer composition	Epoxidized materials	Mixing ratio
Example 9	Example 1	ESO	7: 3
Example 10	Example 1	ESO	5: 5
Example 11	Example 1	ESO	4: 6

Experimental Example  1: Physical property evaluation

Experimental specimens were prepared using the plasticizer compositions of Examples and Comparative Examples described in Tables 1 and 2.

The specimen is prepared by referring to ASTM D638, 40 parts by weight of the plasticizer composition of Examples 1 to 11 and Comparative Examples 1 to 5, 3 parts by weight of stabilizer (BZ-153T) in 100 parts by weight of PVC (LS100S) 3L super mixer ( after mixing at 98 and 700 rpm in a super mixer, and then working with a roll mill for 4 minutes at 160 ° C. to produce 5 mm sheets, press work at 180 ° C. for 2.5 minutes at low pressure and 2 minutes at high pressure, and then make 1T and 3T sheets. Specimen was produced. Each specimen was used to evaluate physical properties according to the test items below, and the results are summarized in Tables 3 and 4 below.

<Test item>

Hardness Measurement

Using ASTM D2240, measurements were taken at 25 ° C. shore (A) hardness, 3T and 10s conditions.

Tensile strength measurement

By the ASTM D638 method, the cross head speed was pulled to 200 mm / min (1T) using a test instrument, UTM (manufacturer; Instron, model name; 4466), and the point where the specimen was cut was measured. . Tensile strength was calculated as follows:

Tensile Strength (kgf / mm2) = Load Value (kgf) / Thickness (mm) × Width (mm)

Elongation (elongation rate) measurement

By using the ASTM D638 method, the crosshead speed was pulled to 200 mm / min (1T) using the U.T.M, and then measured at the point where the specimen was cut, the elongation was calculated as follows:

Elongation (%) = [length after extension / initial length] x 100 was calculated.

Migration loss measurement

Specimens with a thickness of 2 mm or more were obtained according to KSM-3156. A PS plate was attached to both sides of the specimen and a load of 1 kgf / cm ² was applied. The specimen was left in a hot air circulation oven (80 ° C.) for 72 hours and then taken out and cooled at room temperature for 4 hours. Then, after removing the PS attached to both sides of the test piece, the weight before and after leaving in the oven was measured and the transfer loss was calculated by the following equation.

Transfer loss (%) = [(Initial weight of specimen at room temperature-weight of specimen after leaving the oven) / Initial weight of specimen at room temperature] × 100

Measurement of volatile loss

After working the prepared specimen at 80 ℃ for 72 hours, the weight of the specimen was measured.

Heating loss (%) = [(initial specimen weight-specimen weight after operation) / initial specimen weight] x 100.

Stress testing

In the stress test, the specimen was bent at room temperature for a period of time, and then observed the degree of transition (the degree of bleeding), and the degree was expressed as a numerical value, the closer to 0, the better and the closer to 3, the worse. It is a characteristic.

Thermal stability test

The thermal stability of the specimen against high temperature contact was tested by moving 0.5T specimen prepared by roll-mill operation using Mathis Oven at a speed of 10mm / 25sec at 220 ℃.

division	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating loss (%)	Stress test
Example 1	82.5	192.1	337.5	2.58	2.22	0.5
Example 2	77.5	174.6	304.6	3.56	3.40	0
Example 3	84.0	198.5	320.1	2.56	1.88	0
Example 4	85.5	208.7	314.2	1.21	1.20	0.5
Example 5	85.5	220.5	320.4	1.68	1.31	0.5
Example 6	86.0	224.7	318.5	1.56	1.11	0.5
Example 7	80.0	198.6	325.6	2.54	2.43	0
Example 8	85.0	211.1	308.4	2.86	1.77	0.5
Comparative Example 1	84.0	185.3	287.4	3.57	2.48	2.0
Comparative Example 2	78.5	168.4	267.1	4.88	4.50	1.5
Comparative Example 3	82.0	170.5	271.3	5.66	6.58	2.0
Comparative Example 4	87.0	200.7	295.4	3.56	1.50	3.0
Comparative Example 5	83.5	178.5	288.0	3.60	3.20	1.5
Comparative Example 6	83.0	187.0	290.3	4.11	3.87	0.5
Comparative Example 7	81.0	174.5	268.4	5.24	5.79	0.5
Comparative Example 8	83.5	180.2	288.0	5.60	5.81	1.0
Comparative Example 9	85.0	165.5	274.3	3.60	3.47	2.0
Comparative Example 10	87.5	172.3	290.2	3.10	2.58	2.5

division	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating loss (%)	Stress test
Example 9	82.5	214.5	348.0	2.20	1.76	0
Example 10	83.0	228.4	345.8	1.62	1.22	0
Example 11	84.5	208.7	314.2	1.22	1.01	1.5

Referring to Table 3, in Comparative Examples 1 to 5 in which the carbon number of the cyclohexane 1,4-diester-based material is less than 9, the tensile strength and elongation are the same as those in which the same citrate-based material is added. It can be seen that the mechanical properties as well as the transfer loss and heat loss characteristics are very poor. In addition, it can be confirmed that the plasticizer in the resin is easily exuded because the resistance to stress is generally weak.

In addition, in the case where the diester group is bonded to the 1,2 positions instead of the 1,4 position, the tensile strength, elongation, transfer loss, and heating loss are more obvious than the effects of carbon number. It can be seen that the physical property level is poor.

Through this, cyclohexane 1,4-diester is prepared in order to produce a resin having satisfactory physical properties in all aspects of mechanical properties (tensile strength and elongation) and physical properties related to the total amount of plasticizer (transition loss and heating loss). It was confirmed that it is preferable to mix the system material with the citrate material by applying an alkyl group having 9 or more carbon atoms.

In addition, referring to Table 4, Examples 9 to 11 are each added to the epoxidized soybean oil in Example 1 in the ratio of 7: 3, 5: 5, and 4: 6, respectively, It can be confirmed that heating loss and transition loss are excellent, and mechanical properties such as tensile strength and elongation can be obtained at an excellent level.

However, when excessively used, mechanical properties such as elongation and tensile strength may be drastically lowered as in Example 11, and the resistance to stress may be deteriorated. Thus, cyclohexane 1,4 is preferred. -The epoxidation material is preferably contained in an amount of 100 parts by weight or less relative to 100 parts by weight of the mixture of the diester material and the citrate material.

Further, referring to FIG. 1, in Examples 1 and 5 without adding an epoxidation material, it was confirmed that the specimen was burned and burned to a degree close to black, but in Example 9, discoloration was hardly achieved. It can be seen that the naked eye, and accordingly it can be seen that the thermal stability can be improved through the addition of the epoxidized material.

In other words, when the epoxidized material is mixed so as to act as a 'plasticizer' to more than 10 parts by weight, rather than a secondary stabilizer, it can be seen that there are improvements in all physical properties.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

Claims (11)

One cyclohexane 1,4-diester material; And citrate-based materials;

The plasticizer composition of the cyclohexane 1,4-diester-based material and the citrate-based material is 99: 1 to 1:99.

The method of claim 1,

The plasticizer composition of the cyclohexane 1,4-diester-based material and the citrate-based material is 95: 5 to 50:50.

The method of claim 2,

The plasticizer composition of the cyclohexane 1,4-diester-based material and the citrate-based material is 95: 5 to 60:40.

The method of claim 1,

The cyclohexane 1,4-diester-based material is diisononyl cyclohexane-1,4-diester (1,4-DINCH), diisodecyl cyclohexane-1,4-diester (1, Plasticizer composition is a mixture of two or more selected from the group consisting of 4-DIDCH), di (2-propylheptyl) cyclohexane-1,4-diester (1,4-DPHCH).

The method of claim 1,

The citrate-based material is a plasticizer composition comprising any one selected from the group consisting of a 4 to 10 carbon-based alkyl substituted citrate-based material and a 4 to 10 carbon-based non-hybrid alkyl substituted citrate-based material.

The method of claim 1,

The citrate-based material is a non-hybrid alkyl substituted citrate-based material having 4 to 10 carbon atoms,

Plasticizer composition of the alkyl group having 4 to 10 carbon atoms of the citrate-based material is a straight chain or branched chain.

The method of claim 1,

A plasticizer composition further comprising an epoxidation material.

The method of claim 7, wherein

The epoxidation material is a plasticizer composition further comprises 1 to 100 parts by weight based on 100 parts by weight of the mixed weight of cyclohexane 1,4-diester-based material and citrate-based material.

The method of claim 7, wherein

The epoxidized material is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate Plasticizer composition comprising one or more selected from the group consisting of epoxidized oleate, epoxidized tallate and epoxidized linoleate.

100 parts by weight of resin; And 5 to 150 parts by weight of the plasticizer composition of claim 1.

The method of claim 10,

The resin composition is one or more selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer.

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